Chloromethyl Methyl Ether → ethyl 3-tert-butyl-1-{4-[(methoxymethoxy)methyl]benzyl}-1H-pyrazole-5-carboxylate

HRID 507962ノート

反応式

HRID 507962 の反応式
[C:1]([C:5]1[CH:9]=[C:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[NH:7][N:6]=1)([CH3:4])([CH3:3])[CH3:2].Cl[CH2:16][C:17]1[CH:22]=[CH:21][C:20]([CH2:23][OH:24])=[CH:19][CH:18]=1.C(=O)([O-])[O-].[K+].[K+].C(N(C(C)C)C(C)C)C.[CH3:40][O:41][CH2:42]Cl>O1CCCC1.O.CN(C)C=O>[C:1]([C:5]1[CH:9]=[C:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[N:7]([CH2:16][C:17]2[CH:22]=[CH:21][C:20]([CH2:23][O:24][CH2:40][O:41][CH3:42])=[CH:19][CH:18]=2)[N:6]=1)([CH3:4])([CH3:2])[CH3:3]

参加物

9

反応物 5

HCID 7864Chloromethyl Methyl EtherHCID 11430Potassium CarbonateHCID 81531DiisopropylethylamineHCID 2743509Ethyl 3-tert-butyl-1H-pyrazole-5-carboxylateHCID 5107660[4-(Chloromethyl)phenyl]methanol

生成物 1

HCID 23157202ethyl 3-tert-butyl-1-{4-[(methoxymethoxy)methyl]benzyl}-1H-pyrazole-5-carboxylate収率 35.4%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
70 °C

実験手順

A mixture of ethyl 3-tert-butyl-1H-pyrazole-5-carboxylate (3.00 g, 15.3 mmol), [4-(chloromethyl)phenyl]methanol (2.50 g, 16.0 mmol), potassium carbonate (2.11 g, 15.3 mmol) and N,N-dimethylformamide (40 mL) was stirred at 70° C. for 3 hr. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a yellow oil. To a solution of the obtained oil and N-ethyldiisopropylamine (8.0 mL, 46 mmol) in tetrahydrofuran (50 mL) was added chloromethyl methyl ether (4.40 mL, 46.3 mmol) at 0° C., and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated, and the residue was purified by silica gel column chromatography (30% ethyl acetate/hexane) to give the title compound (1.95 g. yield 35%) as a colorless oil.

後処理

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe extract was washed with saturated brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customto give a yellow oil
  6. stirringthe mixture was stirred overnight at room temperature
  7. concentrationThe reaction mixture was concentrated
  8. customthe residue was purified by silica gel column chromatography (30% ethyl acetate/hexane)

出典と根拠

ORDレコード
ord-8f8f354f28b94a0cbb6585050c8f34e0
出典データセット
uspto-grants-2010_08
特許番号
US07786165B2

反応ノート

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